JP2777441B2 - Radiation-sensitive resin composition and pattern forming method using the radiation-sensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application fields> The present invention is suitable for manufacturing, for example, lithographic printing plates, proofs for multicolor printing, color filters used for color video cameras or liquid crystal color TVs, IC circuits, and photomasks. The present invention relates to a novel radiation-sensitive resin composition and a pattern forming method using the radiation-sensitive resin composition.

<Prior Art> Conventionally, as a radiation-sensitive compound for a radiation-sensitive resin using radiation such as visible light, X-ray and electron beam, for example, a compound containing a naphthoquinonediazide compound and a compound containing an aromatic azide compound are known. Have been. However,
These compounds have the disadvantage that their sensitivity is insufficient, since the quantum yields essentially do not exceed 1. For example, the quantum yield of a naphthoquinonediazide system is about 0.2 to 0.3.

Therefore, a method utilizing a chain reaction has been developed as a method for dramatically increasing the quantum yield. One example is a chain reaction by photoradical polymerization, but the photoradical polymerization has a disadvantage that it is affected by oxygen.

On the other hand, as one of the systems using a chain reaction, a chemically amplified resist using a catalytic reaction has been proposed (H. Ito, C, G. et al.
Willson, Polym. Eng. Sci. 23 , 1012, 1983 ). When a compound which generates an acid by radiation, for example, a suitable onium salt (sulfonium salt, iodonium salt) is irradiated with a radiation, an acid is generated, and the acid causes a chain reaction as a catalyst. As a typical example of such a chemically amplified resist, one using a polymer compound having the following structural unit and a radiation-sensitive acid generator is known (H. Ito, C, G. Will.
son, SPIE. 771 , 24, 1987 ; H. Ito, M. Ueda, Macromolecules, 2
1 , 1475, 1988 ).

<Problems to be Solved by the Invention> The above-described resist for chemical amplification shows high sensitivity as compared with naphthoquinonediazide and the like, but has no stability over time, so that it cannot be stored for a long time. Since it is bad, there are various problems that the sensitivity characteristics and the like fluctuate during the period until development and that the sensitivity is still insufficient.

In view of the circumstances described above, the present invention provides a novel radiation-sensitive resin composition having high sensitivity, wide development tolerance during development, and excellent stability over time, and a method for forming a pattern using the radiation-sensitive resin composition. About.

<Means for Solving the Problems> The present inventors have conducted intensive studies to achieve the above object, and as a result, using a compound which generates an acid by irradiation with radiation and a polymer compound having a specific structural unit. As a result, it has been found that a radiation-sensitive resin composition having high sensitivity, wide development tolerance during development, and excellent stability over time can be obtained.

The constitution of the radiation-sensitive resin of the present invention based on such findings is as follows: (a) a compound that generates an acid upon irradiation with radiation, (b) an alkali metal salt of acrylic acid or methacrylic acid, and a compound represented by the following general formula (II). Or a vinyl ether represented by the following general formula (III) in the presence of an acid catalyst by reacting acrylic acid or methacrylic acid with acrylic acid or methacrylic acid. ) (Wherein, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent hydrogen, a lower alkyl group, an aryl group, and an aralkyl group, and R ₄ represents a lower alkyl group, an aryl group, and an aralkyl group. And a polymer compound having a structural unit represented by the formula:

The pattern forming method using the radiation-sensitive resin composition according to the present invention includes: (a) a compound that generates an acid upon irradiation with radiation; and (b) a structural unit represented by the general formula (I). A radiation-sensitive resin composition containing a polymer compound having the formula (I) is applied to a substrate and dried to form a radiation-sensitive resin layer, and the radiation-sensitive resin layer is irradiated with radiation according to a predetermined pattern. The radiation resin layer is heated in the range of 50 ° C. to 180 ° C., and then the radiation sensitive resin layer is developed with a developer.

The present invention has surprisingly found that the problem can be solved by using a polymer compound having the structural unit of the general formula (I).

 Hereinafter, the present invention will be described in detail.

The compound capable of generating an acid upon irradiation (a) in the in the radiation present invention, may be used a number of known compounds and mixtures thereof, for example, (i) halogen onium ^-, ▲ BF ^- ₄ ▼, ▲ PF ^- ₆ ▼, ▲ AsF ^- ₆ ▼, ▲ SbF ^- ₆ ▼, ▲ S
_{^{iF - 6 ▼, ▲ ClO -}} 4 ▼, ▲ CF 3 SO - 4 ▼ salts such as; (ii) organic halogen compounds; (iii) naphthoquinone diazide sulfonic acid compound and (iv) radiation-sensitive acid-generating compound, such as is appropriate It is.

More specifically, (i) examples of ammonium salts as onium salts are described in U.S. Patent Nos. 4,069,055 and 4,069,056; examples of diazonium salts include Photogr. Sci, Eng., 18 387 (1974), J. Macromo
l. Sci., Chem., A21 , 1965 (1984), and Polymer, 21 , 423.
(1980); Examples of iodonium salts include Macromol
ecules, 10 , 1307 (1977), Chem. & Eng. News, Nov. 28, P31
(1988), and EP 0104,143;
Examples of sulfonium salts include Polymer J., 17 , 73 (19
85), Polymer Bull., 14 , 279 (1985). J. Polymer Sci., 1
7 , 977 (1979), J. Org. Chem., 43 ,, 3055 (1978), J. Org. C
hem., 50 , 4360 (1985), JP-A-57-18723, JP-A-56-8428, U.S. Pat. No. 4,760,013, U.S. Pat. No. 4,139,655, U.S. Pat. Patent No. 0297,443; Examples of phosphonium salts include US Pat. Nos. 4,069,055 and 4,069.
69,056 and Macromolecules, 17 , 2469 (1984);
Examples of selenonium salts include Macromolecules, 10 , 1307
(1977) and J. Polymer Sci., Polymer Chem, Ed., 17 , 104.
7 (1979); for examples of arsonium salts, see Proc.
nf. Rad. Curing ASIA p478 Tokyo, Oct. (1988).

Examples of (iii) organic halogen compounds capable of generating an acid upon irradiation with radiation include carbon tetrabromide, iodoform, tribromoacetophenone, a phenyltrihalomethyl sulfone compound described in JP-B-46-4605,
The halomethyltriazine compounds described in JP-B-48-36281, JP-A-53-133428, JP-A-60-105667 and JP-A-60-239736, Angew.Physik, Chem., 2
4 , 381 (1981), J. Phys. Chem., 66 , 2449 (1962),
JP-A-54-74728, JP-A-55-77742, JP-A-59-77742
148784, JP-A-60-3626, JP-A-60-1385
And halomethyloxadiazole compounds described in JP-A-39-239 and JP-A-60-239473.
(Iii) Examples of the naphthoquinonediazide compound include:
1,2-naphthoquinonediazide- (2) -4-sulfonyl chloride can be mentioned. (Iv) Radiation-sensitive sulfonic acid generating compounds include, for example, ester or amide compounds of 1,2-naphthoquinonediazide- (2) -4-sulfonic acid, Polymer Preprints, Japan 35 , 2406 (1986).
Β-ketosulfone compound described in Macromolecules, 2
1 , 2001 (1988), and ester compounds of nitrobenzyl alcohol and arylsulfonic acids described in JP-A-64-18143, European Patents 0,044,115 and 0,199,6.
No. 72, an ester compound of an oxime and an arylsulfonic acid, U.S. Pat.Nos. 4,258,121, 4,371,605, and 4,618,564, an ester compound of an N-hydroxyamide or imide and a sulfonic acid, European Patent 84515 And the ester compounds of benzoin and sulfonic acid described in JP-A Nos. 199,672 and 199,672.

Among the compounds capable of generating an acid upon irradiation with these radiations, the above-mentioned (i) to (vi) which can generate a non-volatile acid in particular.
The onium salt of i) or the radiation-sensitive sulfonic acid-generating compound of (x) is preferred.

These compounds capable of generating an acid upon irradiation with radiation may be used alone or in combination.The amount of the compound added may be 0.1 to the total solid content of the photosensitive composition of the present invention.
It is preferably from 50 to 50% by weight, more preferably from 1 to 30% by weight. This is because if the amount is less than 0.1% by weight, the amount of generated acid is poor and a chain reaction hardly occurs, and if it exceeds 50% by weight, the effect of increasing the amount cannot be expected again.

The polymer compound according to (b) of the present invention is characterized in that it has a structural unit represented by the above general formula (I) in its molecular structure, and a homopolymer having a repeating structure of only the structural unit Or a copolymer obtained by combining the above structural unit with one other vinyl structural unit.

In the general formula (I), R ₂ and R ₃ each represent a hydrogen, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; a substituted or unsubstituted aryl group; R ₄ represents a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; an aralkyl group such as a substituted or unsubstituted aryl group or a benzyl group.

In the polymer compound of the present invention having a copolymer structure, examples of the structural unit used in combination with the structural unit represented by the general formula (I) include ethylenically unsaturated units such as ethylene, propylene, isobutylene, butadiene, and isoprene. Olefins, styrenes such as styrene, α-methylstyrene, β-methylstyrene, β-chlorostyrene, acrylic acid, methacrylic acid, maleic acid,
Aliphatic carboxylic acids such as itaconic acid, crotonic acid, maleic anhydride, methyl maleic anhydride or anhydrides thereof, methyl ester, ethyl ester, propyl ester, butyl ester, amyl ester, ethylhexyl ester, octyl ester of acrylic acid or methacrylic acid Ester, 2-hydroxyethyl ester, 2,2-dimethyl-3-hydroxypropyl ester, 2-hydroxypropyl ester, 5-hydroxypentyl ester, trimethylolpropane monoester, pentaeristol monoester, glycidyl ester, aryl ester, Esters such as benzyl esters, amides of acrylics or methacryls, N-methylolamide, N-ethylamide, N-hexylamide, N-hydroxyethylamide, Amides such as -phenylamide and N-ethyl-N-phenylamide; vinyl ethers such as ethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and phenyl vinyl ether; vinyls such as vinyl acetate, vinyl butyrate and vinyl benzoate Esters, methyl vinyl ketone, ethyl vinyl ketone,
Examples thereof include vinyl ketones such as propyl vinyl ketone, N-vinyl pyrrolidone, N-vinyl carbazole, 4-vinyl pyridine, acrylonitrile, and methacrylonitrile.

 The polymer compound of the present invention is synthesized as follows.

For example, an alkali metal salt of acrylic acid or methacrylic acid is represented by the following general formula (II) (Wherein, R ₂ , R ₃ and R ₄ are the same as described above), or by reacting with chloromethyl ether represented by the following formula: or with acrylic acid or methacrylic acid; (Wherein R ₂ and R ₄ are the same as defined above). A monomer obtainable by reacting a vinyl ether represented by the following formula in the presence of an acid catalyst is homopolymerized according to a conventional method. Alternatively, by polymerizing the monomer and at least one of other vinyl monomers, a polymer compound having a structural unit of the general formula (I) of the present invention can be obtained.

At this time, the charging ratio of each monomer is preferably 5 mol% or more of the monomer of the structural unit represented by the general formula (I).

The radiation-sensitive resin composition of the present invention may contain a known polymer compound for improving the film strength or developability of the radiation-sensitive resin layer. Examples of such a polymer compound include novolak resin, phenol resin, polyvinyl formal resin, polyvinyl butyral resin, polyester resin, epoxy resin, alkyd resin, polyurethane resin, polyamide resin, and natural resin.

The radiation-sensitive resin composition of the present invention can further generate a dye, a printout agent for forming a visible image, a pigment, a plasticizer, a silane coupling agent, a surfactant, and the acid, if necessary. A sensitizer or the like for increasing the acid generation efficiency of the compound can be contained.

Known sensitizers can be used as such a sensitizer,
For example, anthracene, phenanthrene, perylene, pyrene, chrysene, 1,2-benzoanthracene, coronene, 1,6-diphenyl-1,3,5-hexatriene, 1,1,4,
4-tetraphenyl-1,3-butadiene, 2,3,4,5-tetraphenylfuran, 2,5-diphenylthiophene, thioxaton, 2-chlorothioxanthone, phenothiazine, 1,3-diphenylvirazoline, 1,3 -Diphenylisobenzofuran, xanthone, benzophenone, 4-hydroxybenzophenone, anthrone, ninhydrin, 9
-Fluorenone, nitropyrene, 2,4,7-trinitrofluorenone, indanone, phenanthraquinone, tetralone, 7-methoxy-4-methylcoumarin, 3-keto-
Bis (7-diethylaminocoumarin), fluorocene,
Sensitizers such as eosin, rotamine S and triphenylpyrylium perchlorate can be mentioned.

The ratio between these sensitizers and the compound capable of generating the acid is 0.01 / 1 to 10/1 by mole, preferably 0.1 / 1 to 5%.
/ 1.

Further, by using such a sensitizer, the wavelength range felt by the composition of the present invention can be easily extended to visible light.

The radiation-sensitive resin composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and applied on a support.

Examples of such solvents include ethers such as dioxane, diethoxyethane, diethylene glycol dimethyl ether, methyl cellosolve, ethyl cellosolve, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate acetate, and dimethyl oxalate; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolide Pyrrolidones such as, γ-
Lactones such as butyrolactone and sulfoxides such as dimethyl sulfoxide can be exemplified. These solvents may be used alone or in combination of two or more. The concentration (total solid content including additives) in the above components is suitably 2 to 50% by weight.

The radiation-sensitive resin composition of the present invention is applied to a substrate, dried to form a radiation-sensitive resin layer, irradiated with radiation in accordance with a predetermined pattern, and heated at a temperature in the range of about 50 ° C to 180 ° C. It is effective to form a pattern by developing with a developer.

Next, an example of the pattern forming method of the present invention will be described. First,
The resin composition of the present invention is applied on a substrate and dried to form a radiation-sensitive resin layer. Here, as the substrate, silicon, silicon dioxide, silicon nitride, polysilicon, ceramics, aluminum, copper, aluminum oxide, glass, ITO, plastic film, paper, etc. are used according to the purpose.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain coating can be used. Then, after applying the resin composition to the substrate, the applied substrate is heat-treated at about 20 ° C to 150 ° C. This heat treatment is performed to reduce the concentration of the solvent in the resin composition, but the preferred range of the heat treatment is 50 to 120 ° C.
For 30 seconds to 30 minutes. This heat treatment is preferably performed until the rate of change in solvent removal is relatively small,
The temperature and the time are appropriately set depending on the properties of the resin composition, the type of the solvent, the application amount, and the like.

As the radiation to be applied, visible light, ultraviolet light, X-rays, and electron beams can be used. Examples of these radiation sources include visible and ultraviolet light sources such as fluorescent lamps, carbon arc lamps, mercury lamps, chemical lamps, xenon lamps, metal halide lamps, KrF-excimer lasers, XeCl-excimer lasers, and ArF-excimer lasers, and electron beam excitation. , Plasma radiation and X-ray radiation such as synchrotron radiation.

A method of irradiating by scanning with an energy beam can also be used in the present invention. Such laser beams include a helium / neon laser and an argon laser. A laser such as a krypton ion laser, a helium / cadmium laser, and a dye laser, or an electron beam such as a thermionic emission gun or a field emission gun can be used.

Next, the radiation-sensitive resin layer is in a range of about 50 ° C to 180 ° C,
Preferably, heating is performed in the range of 60 ° C to 150 ° C. According to the infrared absorption spectra of Examples 1 to 4 described below, the heat treatment after the irradiation changes the structural unit represented by the general formula (I) into a structural unit containing a carboxylic acid in the portion irradiated with the radiation. Indicated.

Subsequently, a pattern is obtained by developing with a developing solution, and a positive or negative pattern can be obtained depending on the type of the developing solution used.

A positive pattern can be obtained by using an alkaline aqueous solution as a developer.

Examples of the alkaline aqueous solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and sodium tertiary phosphate, ethylamine, and n-amine. Alkylamines such as propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine; alcoholamines such as diethanolamine and triethanolamine; tetramethylammonium hydroxide;
Examples include quaternary ammonium salts such as tetraethylammonium hydroxide and trimethyl (2-hydroxyethyl) ammonium hydroxide, and aqueous solutions of cyclic amines such as pyrrole and piperidine.

If necessary, other additives such as a surfactant, a wetting agent, a stabilizer and a small amount of an organic solvent can be added to the developer.

The negative pattern can be obtained by using an organic solvent as a developer. The organic solvent used here depends on the type of the copolymer.

Examples of the organic solvent include dichloromethane, chlorobenzene, toluene, acetone, methyl ethyl ketone, diethyl ketone, isopropanol, anisole,
Butyl acetate, a mixed solvent thereof, or a mixed solvent thereof such as hexane can be used as appropriate.

<Examples> Next, the present invention will be described in more detail with reference to examples.

(Synthesis Example) Synthesis Example 1 (Synthesis of Polymer Compound A) 112.2 g of potassium t-butoxide was added to tetrahydrofuran
86.1 g of methacrylic acid is gradually added dropwise to the solution suspended in 1000 ml to obtain potassium methacrylate.

Next, add 76.5 g of methylchloromethyl ether,
The reaction was allowed to proceed overnight at room temperature. The reaction mixture was poured into 5 l of water, extracted with ether, and the ether layer was washed with water.
It was dried over anhydrous magnesium sulfate.

Then, ether was distilled off, followed by distillation under reduced pressure to obtain 120 g of a liquid having a boiling point of 60 to 65 ° C / 20 mmHg.

The obtained liquid is based on the following spectral data:
It was identified as methoxymethyl methacrylic acid of the following structural formula (1).

Infrared absorption spectrum: See Fig. 1. Nuclear magnetic resonance spectrum: 10 g of methoxymethyl methacrylic acid and 0.06 g of α, α'-azobisisobutyronitrile obtained above were dissolved in 10 ml of toluene, and the mixture was purged with nitrogen gas and heated at 80 ° C. for 6 hours.

The solution was cooled, poured into 500 ml of hexane, and the resulting white precipitate was filtered and dried to obtain 9.3 g of a white polymer.

The infrared absorption spectrum of the obtained white polymer was measured, and it was confirmed to be the polymer compound A (see FIG. 2).

Synthesis Example 2 (Synthesis of polymer compound B) 30.0 g of methacrylic acid and 50.3 g of vinyl ethyl ether were dissolved in 450 ml of ethylene dichloride. When 0.1 g of paratoluenesulfonic acid was added to this solution, the solution generated heat and became reddish. After stirring for 1 hour, triethylamine 3ml
Was added to stop the reaction.

The obtained reaction mixture was washed with water and dried over anhydrous magnesium sulfate.

Then, ethylene dichloride was distilled off, followed by distillation under reduced pressure to obtain 33 g of a liquid having a boiling point of 50 to 53 ° C./10 mmHg.

The obtained liquid was identified as α-ethoxyethyl methacrylic acid of the following structural formula (2) by the following spectrum data.

Infrared absorption spectrum: See Fig. 3 Nuclear magnetic resonance spectrum: Α-ethoxyethyl methacrylic acid 10 g obtained above
Then, 0.06 g of α, α'-azobisisobutyronitrile was dissolved in 10 ml of toluene, and the atmosphere was replaced with nitrogen gas, followed by heating at 80 ° C. for 6 hours.

The solution was cooled, poured into 500 ml of hexane, and the resulting white precipitate was filtered and dried to obtain 9.0 g of a white polymer.

The infrared absorption spectrum of the obtained white polymer was measured, and it was confirmed to be a polymer compound B (see FIG. 4).

Synthesis Example 3 (Synthesis of Polymer Compound C) In the synthesis of methoxymethyl methacrylic acid in Synthesis Example 1, by using 156.6 g of chloromethylbenzyl ether instead of methylchloromethylether, the boiling point was 94 ° C.
150 g of a liquid at 9696 ° C./4 mmHg was obtained.

The obtained liquid is based on the following spectral data:
The compound was identified as benzyloxymethyl methacrylic acid of the following structural formula (3).

Infrared absorption spectrum: See Fig. 5 Nuclear magnetic resonance spectrum: Polymerization was performed in exactly the same manner as in Synthesis Example 1, and the absorption spectrum of the obtained polymer was measured to confirm that it was a polymer compound C (see FIG. 6).

Synthesis Example 4 (Synthesis of polymer compound D) 5.0 g of methoxymethyl methacrylic acid synthesized in Synthesis Example 1
(0.0385 mol), 4.0 g (0.0385 mol) of styrene and α,
After dissolving 0.06 g of α'-azoisobutyronitrile in 9 ml of toluene and purging with nitrogen gas, the mixture was heated at 80 ° C. for 5 hours.

After cooling, the reaction mixture was diluted with 20 ml of dichloromethane, and the solution was poured into 500 l of hexane, and the resulting white precipitate was filtered and dried to obtain 5.9 g of a white polymer.

The copolymerization ratio of the obtained white polymer was styrene / methoxymethyl methacrylic acid = 52/48 as determined from the acid value after hydrolysis with an acid.

Further, the infrared absorption spectrum of the white polymer was measured, and it was confirmed that the polymer was polymer compound D (see FIG. 7).

Synthesis Examples 5 to 7 (Synthesis of Polymer Compounds E, F, and G) By operating in exactly the same manner as in Synthesis Example 4, the above polymer compounds E, F,
G was synthesized. These infrared absorption spectra are shown in FIG. 8 (polymer compound E), FIG. 9 (polymer compound F),
The results are shown in FIG. 10 (polymer compound G).

Examples 1 to 4 7.0 g of the polymer compound shown in Table 1 below and 0.35 g of the radiation-sensitive acid generator were mixed with diethylene glycol dimethyl ether 9
The solution was dissolved in 2.65 g, and this solution was passed through a 0.2 μm membrane filter to prepare a radiation-sensitive resin composition.

These compositions were applied to a rock salt plate using a spinner so that the dry applied film thickness became 1 μm, and dried at 85 ° C. for 30 minutes.

The film was irradiated (10 mj / cm ² ) using a 100 W low-pressure mercury lamp (UL2-1BQ-W1 manufactured by Ushio Inc.) as a radiation source.

The irradiated film was heated at 105 ° C. for 10 minutes. FIGS. 11 to 14 show the respective infrared absorption spectra of the resin film before and after heating after the irradiation. In the figure, (a) shows an infrared absorption spectrum before heating, and (b) shows an infrared absorption spectrum after heating.

As shown in FIGS. 11 to 14, these infrared absorption spectra indicate that a carboxyl group was generated by heating.

Examples 5 to 7 On a brush-polished aluminum plate anodized, 14.0 g of the polymer compound shown in Table 2 below, 0.7 g of triphenylsulfonium trifluoromethanesulfonate and 0.7 g of perylene were added.
A radiation-sensitive composition obtained by dissolving 13 g of diethylene glycol dimethyl ether in 185.3 g was applied with a wheyer and heated at 70 ° C.
Dry for 20 minutes.

The dry coating amount at this time was 1.9 to 2.0 g / m ² .

The lithographic printing plate material thus obtained was irradiated in close contact with a high-pressure mercury lamp through a step tablet (density difference 0.15 g, 21 steps, No. 2 manufactured by Eastman Kodak Co.), and then
After heating at 105 ° C. for 10 minutes, development was performed at 25 ° C. for 60 seconds using a 2-fold dilution of a negative PS plate developer DN-3C (manufactured by Fuji Photo Film).

The sensitivity was evaluated by setting the irradiation time at which the fifth stage in the gray scale was completely clear as an appropriate irradiation time.

As a comparative example, a positive PS plate FPS manufactured by Fuji Photo Film Co., Ltd. was used, and a positive PS plate developer (Fuji Photo Film Co., Ltd.) was used as a developing solution. Shows the clearing time.

From Table 2, positive PS using the radiation-sensitive composition of the present invention
It can be seen that the plate is 60 to 110 times more sensitive than the conventional positive PS plate.

In addition, when the printing plates of Examples 5 to 7 were printed using a sheet-fed offset printing press, good printed matters were obtained.

Further, the PS plate of Example 6 was examined for a change in sensitivity with time after irradiation. As a result, there was no change in sensitivity between heating and developing after 5 minutes from irradiation and heating and developing after one day.

Example 8 Radiation-sensitive resin composition The above radiation-sensitive resin composition was applied to a silicon wafer with a spinner and dried at 85 ° C. for 30 minutes. At this time, the film thickness was 1.0 μm.

The resin film was irradiated with KrF-excimer laser,
After heating at 10 ° C. for 10 minutes, dip development was performed with an alkali developing solution NMD-3 (manufactured by Tokyo Ohka) (at 25 ° C. for 60 seconds).

The characteristic curve is shown in FIG. 15, and it can be seen that the sensitivity is very high and there is almost no film loss.

Further, by pattern irradiation using a KrF-excimer laser stepper having a numerical aperture of 0.37, a 0.35 μm line-and-space pattern could be clearly resolved.

Example 9 A lithographic printing material was obtained from the following radiation-sensitive composition in exactly the same manner as in Examples 5 to 7.

A 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka, NMD-3) was used as a developer, and the time required for the step tablet to clear 5 steps was 30 seconds. Further, when this printing plate was printed by using a sheet-fed offset printing machine, a good printed matter was obtained.

Examples 10 and 11 A radiation-sensitive resin composition having the composition shown in Table 3 was applied to an anodized brush-polished aluminum plate with a wheyer.
Dry at 70 ° C. for 20 minutes. The dry coating amount was about 2.0 g / m ² . The plate material was irradiated with a step tablet and a negative image in close contact with a high-pressure mercury lamp, then heated at 105 ° C. for 10 minutes and developed with a developing solution shown in Table 3 to obtain a clear negative image.

As described above, since the appropriate irradiation time of the commercially available negative PS plate (FNS manufactured by Fuji Photo Film) is 90 seconds, it is understood that the resin composition of this example has high sensitivity.

<Effects of the Invention> As described in detail with the examples above, according to the present invention, a photosensitive resin composition having high sensitivity, having a wide development tolerance during development, and having excellent stability over time, and the resin composition are provided. It is possible to provide a pattern forming method for forming a good pattern used. The photosensitive linear resin composition is suitable for producing, for example, a lithographic printing plate, a calibration plate for multicolor printing, a color filter used for a color video camera or a liquid crystal color TV, an IC circuit, and a photomask.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of methoxymethyl methacrylic acid, FIG. 2 is an infrared absorption spectrum of polymer compound A,
3 is an infrared absorption spectrum of α-ethoxyethyl methacrylic acid, FIG. 4 is an infrared absorption spectrum of polymer compound B, FIG. 5 is an infrared absorption spectrum of benzyloxymethyl methacrylic acid, and FIG. 7 shows an infrared absorption spectrum of polymer compound D, FIG. 8 shows an infrared absorption spectrum of polymer compound E, and FIG. 9 shows an infrared absorption spectrum of polymer compound F. FIG. 10 is an infrared absorption spectrum of the polymer compound G, and FIG.
FIG. 12 (a), FIG. 13 (a) and FIG. 14 (a) show the embodiment.
11 (b), 12 (b), 13 (b), and 14 (b) show the same infrared absorption spectra of the resin film after irradiation at 1, 2, 3 and 4. FIG. 15 is a graph showing the characteristic curve of the resin obtained in Example 8 after infrared irradiation spectra of the resin film after irradiation and heating in Examples 1, 2, 3 and 4.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-103611 (JP, A) JP-A-2-25850 (JP, A) JP-A-2-19847 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03F 7/039

Claims (2)

(57) [Claims] 1. A reaction between (a) a compound which generates an acid upon irradiation with radiation, (b) an alkali metal salt of acrylic acid or methacrylic acid, and chloromethyl ether represented by the following general formula (II): Or having a structural unit represented by the following general formula (I) obtained by reacting acrylic acid or methacrylic acid with a vinyl ether represented by the following general formula (III) in the presence of an acid catalyst: A radiation-sensitive resin composition comprising a polymer compound. (Wherein, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent hydrogen, a lower alkyl group, an aryl group, and an aralkyl group, and R ₄ represents a lower alkyl group, an aryl group, and an aralkyl group. ) 2. A reaction between (a) a compound generating an acid upon irradiation with radiation, (b) an alkali metal salt of acrylic acid or methacrylic acid, and chloromethyl ethers represented by the following general formula (II): Or having a structural unit represented by the following general formula (I) obtained by reacting acrylic acid or methacrylic acid with a vinyl ether represented by the following general formula (III) in the presence of an acid catalyst: A radiation-sensitive resin composition containing a polymer compound is applied to a substrate and dried to form a radiation-sensitive resin layer, (Wherein, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent hydrogen, a lower alkyl group, an aryl group, and an aralkyl group, and R ₄ represents a lower alkyl group, an aryl group, and an aralkyl group. Irradiating the radiation-sensitive resin layer with radiation according to a predetermined pattern, heating the irradiated radiation-sensitive resin layer in a range of 50 ° C. to 180 ° C., and then developing the radiation-sensitive resin layer with a developer. A pattern forming method using a radiation-sensitive resin composition, characterized by comprising: